Metallisable polyazo dyestuffs



United States Patent I Claims priority, application Switzerland June 10, l95

7 Claims. or. 260-172) The present invention is concerned with the production of metallisable polyazo dyestufis which have an aflinity to cellulose fibres. It is also concerned with the production of dyestuffs containing heavy metal in complex linkage by treating the new polyazo dyestuffs or the intermediate products used to produce the new dyestuifs with agents giving otf metal, in particular with agents giving elf copper. Finally it is also concerned with the attain ment of very fast, metal containing dyeings on cellulose material with the aid of the new polyazo dyestuffs.

A process is already known for the production of disand poly-azo dyestuffs which consists in coupling acetoacetylamino-hydroxynaphthalene compounds which can be twice coupled with two mols of the same diazonium componnd ,of the benzene and naphthalene series, and also'of monoazo dyestuffs. -If suitable components are chosen, metallizable disazo and polyazo dyestuffs are ob.- tained which are symmetrical with regard to the azo component. These dyestuffs are suitable for the fast dye.- ing of mixtures made up from animal and vegetable fibres. A modification of this process consists in first acylating the hydroxyl group in the acetoacetylaniinohydro tynaphthalene compound and then coupling 1 mol of a diazo component at the acetoacet-yl radical whereupon the acyloxy group in the rnonoazo dyestufi formed is saponified to the hydroxyl group and the compound so obtained is then reacted with 1 mol of a diazonium compound different from the first. This modification leads to dyestuffs which, with regard to the azo corn.- ponen't, are unsymmetrical.

It has now been found that new, unsymmetrical:- with regard to the acetoacetylamino-hydroxynaphthalene compound-wery valuable metallizable or metalcont-aining dyestuffs can be produced directly if a tetrazotized 4.4- di an1inodipheny1"compound having a ,snbstitnerit capable of forming ametal complex in both o-positions to the diazo groups, is coupled in an alkaline niedinm with an eqnimolecular amount of both a hydroxynaphthalene sulphonic acid and an azo dyestulf, and, if desired, the polyazo dyestufi obtained or an intermediate compound used to form the same is converted into the "complex heavy metal compound. The no dyestuff used for the formation of the polyazo dyestufi" is 'obtained from an acetoacetylamino-hydroxynaphthalene compound with this acylamino group bound either directly or by way of a bridging member to the naphthalene radical, by coupling it in a weakly acid, neutral to weakly alkaline medium with an o-carboxyor, preferably, an o-hydroxydiazo compound of the benzene .or naphthalene series.

The new polyazo dyestuffs which are unsymmetrical ith regard t the .1 po en o pht alene series whi h i c p of up n wi icor espond t he ene al F r a 2,762,794 Patented Sept. 11, 1956 ICQ wh e n:

A represents the radical of a hydroxynaphthalene monoor poly-sulphonic acid, X represents a substituent capable of forming a metal o a x,

Y represents the direct linkage or a bridging member of wherein Ph represents a phenylene radical, Cy represents a l.3.5,-tr iazinyl radical and Z represents a halogen atom, a hydroiiyl group or an amine radical, and represents the" radical of a diazo compound of the benzene 'pr' naphthalene series which can be further substr ted if desired and which contains a carboxyl o r, erably a hydroxyl group in the o.-position to the I (01 9- If desired the aromatic rings can contain the further snbstituents usual in azo dyestuffs, e. g. halogen, alkyl, hydroXyI, alkoxy, nit-r0, acylamino, arylamino, carbonyl, sulphonic acid, sulphonic acid amide, .aryl or alkylsulp'honyl, alkoyl and aroyl groups. Also the naphthalene radical in the above formula can contain preferably sulphonic acid groups whilst the radical B in particular, and also if desired, the'phenyl radicals of the bridging member :Y or the radical A can have further substituents.

The fundamental observation of the process according to .thepresent'invention is that, insofar as diazo components 'of slight coupling energy are used, in particular the .o-hydrOXyaminQ and if desired, also o-carboxyamino compounds ofthe benzene and naphthalene series which form diazoxides, it is not necessary to proceed by way of the corresponding acyloxy dyestuffs to produce the monoazo dyestuffs of the general Formula II tn wherein the symbols havethe samemeaning as given in Formula ;I, which are necessary to form the new polyazo dyestuffs. "With favorably chosen conditions the monoazo dyestu fi coupling at the acetoacetyl radical is well QdefinedQ This process not only enables asymmetrical polyazo dyestufis .of the general Formula I to be produced in a very ifmple manner but rather it is only because of this process that these .dyestufis are accessible at all and/or can be produced uniformly, as in many cases of monoa zo dyestuffs produced by way of the o-acyl derivatives, it is not possible to ,saponify the acyl radical without the monoazo dyestuif being partly, often very greatly split again, apparently with primary splitting off of the acetoacetyl radical.

Suitable coupling components for the production of the monoazo dyestuffs of the Formula II usable accor ng to the present invention are obtained from such aminohydroxynaphthalenecompounds, in particular from aininohydroxynaphthalene sulphonic acids which couple o i t th h r up o t e aphg'afteracylation of theamino group. For

- amino-, 4.6-dichloro-,

example, derivatives of 1-amino-7-hydroxynaphthgalene and its 3- or 4-sulphonic acids, l-amino-S-hydroxynaphthalene-3.6- or 4.6-disulphonic acids, 2-amino-6-hydroxynaphthalene-S-sulphonic acid and in particular, 1- or 2- amino-S-hydroxynaphthalene-7-sulphonic acids and 2- amino-S-hydroxynaphthalene-6-sulphonic acid as well as the 3'- or 4-aminobenzoyl and 3'- or 4'-aminophenyl carbamyl derivatives thereof. If these compounds, which contain a primary amino group, are reacted preferably in the aqueous solution of their alkali salts, with diketene until the primary amino group disappears, then corresponding acetoacetylamino compounds are obtained which can be used as coupling components. In addition, the products of the reaction in steps of the listed aminohydroxynaphthalene sulphonic acids with cyanuric chloride, an acetoacetylamino-amino compound of the henzene series and, if desired, a further amine, can be used. Diazo components which can be used for the production of monoazo dyestuffs of the general Formula II are for example: Z-aminobenzene-l-carboxylic acid, 4-chloroor S-nitro-Z-aminobenzene-l-carboxylic acid, Z-aminobenzene-l-carboxylic acid-S-sulphonic acid or -5-sulphonic acid amide, 2-arninonaphthalcne-3-carboxylic acid. The o-hydroxyamino compounds of the benzene series are particularly suitable diazo components. As examples can be named: 2-amino-l-hydroxybenzene, 4-methyl-, 4-chloro-, 5- or 4-nitro, 4-1nethylsulphonyl-, 4-acetyl-, 4-acetyl- 4.6-dinitro, 4-methylor -chloro- 6-nitro, 6-methylor -chloro-4-nitro-, 4-tert. amyl-6-nitro-, 4-acetylamino-6-nitro-, 6-acetylamin0-4-nitro-, 4-methylor -chloro-5-nitro-2-amino-l-hydroxybenzene, 4-methyl-, 4-chloro-4-nitroor 4-benzoylamino-2-amino-l-hydroxybenzene-6-sulphonic acid, 6-methyl-, 6-chloro-, 6-nitro-, G-benzoylamino-Z-amino-l-hydroxybenzene 4 sulphonic acid, 3-amino-2-hydroxybenzene-l-carboxylic acid-S-sulphonic acid, 4-hydroxy-3-aminobenzene-l-carboxylic acid, 4-hydroxy-3-aminobenzene-l-sulphonic acid or -sulphonic acid amide, -sulphonic acid methylamide, -sulphonic acid dimethylamide, -sulphonic acid diethylamide, -sulphonic acid oxethylamide. Also l-amino-Z-hydroxynapthalene- 4- or -6-sulphonic acid and 6-nitronaphthalene-l.Z-diazoxide.-4-sulphonic acid can be used.

A too strongly alkaline medium should be avoided in the production of monoazo dyestuffs of the Formula II because this favors the naphthol coupling. It is of ad vantage to determine the most favorable coupling conditions which are dependent on the coupling energy of the diazo component from case to case by a series of trials. Sometimes it is advisable before using the monoazo dyestuff, to free it by redissolving from any naphthol cou pling product present.

The following 4.4'-diaminodiphenyl compounds having substituents capable of forming a metal complex can be used to build up the polyazo dyestuffs according to the present invention: 4.4'-diaminodiphenyl-3.3-dicarboxylic acid, 4.4'-diamino-3.3-dimethoxydiphenyl, 4.4-diamino- 3.3'-di-(carboxymethyloxy)-diphenyl and if desired also 4.4-diamino-3.3'-dihydroxydiphenyl. Because of the greater coupling energy required, the first named compounds are to be preferred to the last named. The tetrazotization of these 4.4-diaminodiphenyl compounds is performed in the usual manner in mineral acid solution or suspension with sodium nitrite in the cold.

It is of advantage to couple the tetrazo compound of the diphenyl series in the first step with the equimolecular amount of a naphthol sulphonic acid. In general, polysulphonic acids are advantageous, in particular l-hydroxynaphthalene-disulphonic acids such as l-hydroxynaphthalene-3.6-, -4.8- and in particular the 3.8-disulphonic acid. If desired however, also l-hydroxynaphthalene- 3.6.8-trisulphonic acid, 2-hydroXynaphthalene-3.6- or -6.8- disulphonic acid or 1.8-dihydroxynaphthalene-3.6-disulphonic acid can be used. If the monoazo dyestuff of Formula II is suitably substituted, also naphthol 'mono-' sulphonic acids can be used, e. g. l-hydroxynapthalene-4- or -5-sulphonic acid or 2-hydroxynaphthalene-4-, -6-, -7- or -8-sulphonic acid. Also aminonaphthol-sulphonic acids can be used such as for example, Z-amino-S-hydroxynaphthalene-7-sulphonic acid, Z-amino-S-hydroxynaphthalenefi-sulphonic acid or 1-amino-8-hydroxynaphthalene-3.6- or -4.6-disulphonic acid. Compounds which are substituted in the amino group by an acyl or aryl group are also favorable such as, e. g. 2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid, 2 acetylamino-S-hydroxynaphthalene-6-sulphonic acid or 2-(3'-sulphophenyl)-amino- 5-hydroxynaphthalene-7-sulphonic acid or 2-(3'-sulphophenyl) -amino-S-hydroxynaphthalene 6 sulphonic acid. The coupling is performed advantageously in the cold with the aqueous solution of the alkali metal salts in the presence of sodium carbonate. It is generally completed very quickly.

The coupling of the diazomonoazo dyestufi in the second step with an equimolecular amount of a monoazo dyestuff of the Formula II which, advantageously, should contain at least one acid water solubilizing group, e. g. carboxyl and preferably sulphonic acid groups, is also performed in the cold inaqueous alkaline solution or suspension. If necessary the coupling can be accelerated by the addition of tertiary nitrogen bases such as pyridine bases, trialkyl or tertiary alkanolamine bases.

The new polyazo dyestuffs of the general Formula I are obtained in the form of their water soluble alkali metal salts as dark powders which dissolve in water with a greyviolet, grey-blue to grey-green colour according to the composition. As such or in the form of their complex heavy metal compounds, if desired after metallizing on the fibre, they dye cellulose material in fast grey-violet, grey-blue to grey-green shades.

To produce the complex heavy metal compounds in substance, it is advantageous to treat the dyestuffs with agents giving off copper in a weakly acid, neutral or alkaline medium, e. g. with copper salts such as copper sulphate, advantageously in the presence of sodium acetate, with copper acetate or with cupritetramrnine salts such as cupritetrammine sulphate, or with copper salts in the presence of stronger organic nitrogen bases such as trialkylamine or alkanol amine bases. If desired the complex heavy metal compounds can also be produced by the use of salts of different heavy metals, e. g. cobalt and copper salts. The reaction can be performed at once or in steps. Also the polyazo dyestuffs according to this invention can be only partly metallized previously, then dyed and then metallized afterwards on the fibre. For the production of partly metallized dyestuffs and those metallized with different metals, it is advantageous to use the monoazo dyestuff of the general Formula II in the pro-, duction of the polyazo dyestuffs according to the present invention in the form of its previously metallized complex heavy metal compound, e. g. in the form of the cobalt or copper compound and then metallize the end product of the coupling in substance or on the fibre with an agent giving off the same or a different heavy metal. The aftertreatment of the cellulose dyeings is done advantageously with copper salts. The coppering of the direct cellulose dyeings either free from metal or partly metallized, can be performed in the dyebath or in a fresh bath in a neutral to weakly acid medium with the usual copper salts such as e. g. copper sulphate or copper acetate. If desired also copper compounds which are stable to alkalies can be used such as are obtained from the reaction of copper sulphate with sodium tartrate in a soda alkaline solution. The cellulose dyeings of the copper containing dyestuffs according to the present invention are distinguished by their very favorable behaviour to anti-crease processing.

The following examples illustrate the invention without limiting it in any way. Parts are given as parts by weight and the temperatures are in degrees centigrade. The relationship ofparts by weight to parts by volume is'as' that of kilogranunes to litres.

- solves in warm water and in concentrated sulphuric acid Example 1 droxybenzene-l-sulphonic acid the following compounds 18.9 parts of 3-amino-4-hydroxybenzene-l-sulphonic acid are diazotized in the usual manner. The clear diazo solution is poured gradually into a solution of 32.3 parts of 2-acetoacetylamino-8-hydroxynaphthalene-6-sulphonic 5 acid and 18 parts of sodium carbonate in 700 parts of water. The dyestuif formation is complete after a few hours. The yellow monoazo dyestuff obtained is precipitated by the addition of 20% by volume of sodium chloride, isolated, and washed with 15% salt solution. It dissolves in water and in concentrated sulphuric acid with a yellow color.

2 acetoacetylamino 8 hydroxynaphthalene 6 sulphonic acid is obtained by reacting diketene with the aqueous solution of the sodium salt of 2-amino-8-hydroxynaphthalene-G-sulphonic acid. The reaction is performed at room temperature until the primary amino group dis- 18.8 parts of 3-amino-4-hydroxybenzene-l-sulphonic acid amide or 18.7 parts of 3-amino-4-hydroxybenzene-l-methylsulphone or 22.3 parts of 5chloro-4-hydroxy-3-aminobenzene-l-sulphonic acid.

If in this example the 1-hydroxynaphthalene-3.8-disulphonic acid is replaced by 31.9 parts of l-hydroxynaphthalene-4.8-disulphonic acid, 31.9 parts of l-hydroxynaphthalene-3.6-disulphonic acid or 33.5 parts of 1.8-dihydroxynaphthalene-3.6-disulphonic acid, 31.9 parts of 2- hydroxynaphthalene-3.6-disulphonic acid, 23.9 parts of 2- hydroxynaphthalenelor -6-sulphonic acid or 39.9 parts wise the same procedure is followed, copper containing trisazo dyestuifs are obtained which also d-ye cellulose material in greenish-grey shades having similar good fastness properties.

are used and otherwise the same procedure is followed:

of 1-hydroxynaphthalene-3.6.8-trisulphonic acid and other- 1 appears.

Example 2 has OH QHSO OOH; OH

, CO-OH: l w Hots -.NH-o 0-CHN=N OgH To form the trisazo dyestuif, the tetrazo solution from The diazo compound of 13.7 parts of 2-aminobenzene- 24.4 parts of 4'.4'-diarnino-3.3-dimethoxydiphenyl is prol-carboxylic acid is coupled in an aqueous solution in the.

presence of 26 parts of sodium carbonate with 32.3 parts duced and then poured at 0-5 into a solution of 31.9 parts 0 of 2-acetoacetylamino-5-hydroxynaphthalene-7-sulphonic of 1 hydroxynaphthalene 3.8 disulphonic acid and parts of sodium carbonate in 1000 parts of water. The acid. The yellow monoazo dyestuff formed is coupled.

formation of the diazomonoazo dyestufi is completed under the same conditions as described in Example 1 with after a short time and no tetrazonium compound can be the coupling product of the tetrazo compound of 24.4 traced. The solution of the yellow monoazo dyestufl departs or 4.4'-diamino-3.3-,dimethoxydiphenyl with 31.9 scribed in the first paragraph in 1000 parts of-water is 40 parts of l-hydroxynaphthalene-4.8-disulphonic acid. The

then poured at 30 into the above diazomonoazo dyestuff coupling is performed in the presence of sodium carboin the presence 'of sodium carbonate while allowing the nate and the trisazo dyestuff is obtained. The copper temperature to rise slowly to 20. After a few hours, the complex compound obtained therefrom according to the coupling is complete. The trisazo dyestulf formed of the method described in Example 1 dyes cotton and staple formula: 0 fibre directly in vivid greenish-grey shades which have HOlS OH OCH: OCH: OH OH is precipitated by the addition of sodium chloride, isolated good wetfastness and very good light fastness properties.

and the damp filter cake is dissolved in 1000 parts of water The cellulose dyeings are distinguished by their very at90". The mixture of 300 parts of a monomolar copper favourable behaviour in anti-crease processing. The copsulphate solution and 150 parts of a 20% ammonium hyper containing dyestuff obtained by the use of the same droxide solution is then added and the whole is stirred number of parts of l-hydroxynaphthalene-3.S-disulphonicj. for 12 hours at 90-95". The dyestuff is isolated by the acid has similar properties, addition of 25% by volume of sodium chloride, the If instead of 13.7 parts of Z-aminobenzene-l-carboxylic precipitate is filtered 01f, washed with 15 salt solution acid, 21.6 parts of 2-aminobenzene-l-carboxylic acid -5- and dried. sulphonic acid amide or 30.3 parts of 5-amino-4-hydroxy- 3-benzoylamino-l-sulphonic acid are used and otherwise the same procedure is followed,dyestuifs are obtained It dyes cotton and other celluwhich dye cellulose material in blue to greenish-grey The copper-containing trisazo dyestutf so obtained dis- With a green-grey color.

lose material directly in greenish-grey shades and the shades. The dyeings have good fastness properties and dyeings have good fastness to washing and water and also excellent stability to anti-crease processing.

very good fastness to light. The viscose dyeings are If in this example the Z-acetoacetylamino-S-hydroxychiefly distinguished by an excellentfastness to anti-creasenaphthalene-7-sulphonic acid is replaced by 32.2 parts of processing. 1 acetoacetylamino -'5 hydroxynaphthalene 7 sul- .Trisazo dyestuffs which also dye cotton and regenerphonic acid and the same procedure is followed, copper ated cellulose in greenish-grey shades with similar fastcontaining trisazo dyestu-fis are obtained which dye cotton ness properties are obtained if instead of 3-amino-4-hyin grey shades with similar fastness properties.

. my i non m CHO 0011, on I SOIH (JO-CH:

NH-oo- HN==N 01H The yellow monazo dyestuif obtained with the diazo If in this example, the 1-acetoacetylamino-8-hydroxycompound from 23.4 parts of -nitro-3-amino-2-hydroxynaphthalene-3.6-disulphonic acid is replaced by 67.9 parts benze'ne-l-sulphonic acid and 32.3 parts of Z-acetoacetylof the condensation product produced in the known manamino 6-hydroxynaphthalene-8-sulphonic acid is coupled ner from 31.9 parts of 1-amino-S-hydroxynaphthaleneinan aqueous solution containing sodium carbonate as 3.6-disulph0nic acid, 18.4 parts of cyanuric chloride, 19.2 described in Example 1, to form the trisazo dyestufi with parts of l-amino-4-acetoacetylaminobenzene and 9.3 parts the coupling product of the tetrazo compound of 24.4 of aminobenzene or 12.4 parts of amino-p-methoxybenparts of 4.4'-diamino-3.3-dimethoxy-diphenyl and 31.9 zene and otherwise the same procedure is followed then parts of l-hydroxynaphthalene-3.8-disulphonic acid. The a copper containing trisazo dyestufi is obtained which trisazo dyestufi is then converted into its copper complex dyes cellulose fibres in blue-grey shades which have simicompound. The copper containing dyestuflf dyes cotton lar good fastness properties.

I Example 5 110:5 on onto 0on- 0H 7 OH CO-CH| =N NH-O o-orrN=N soar Hols mac-o 0C and staple fibre directly in greenish-grey shades which A diazo solution from 18.9 parts of 4-hydroxy-3-aminohave good washing and water fastness and very good benzene-l-sulphonic acid is poured slowly at 05 into an light fastness properties. They are excellently stable to aqueous solution of 44.2 parts of 2-(3'-acetoacetylanti-crease processing. amino) benzoylamino 5 hydroxynaphthalene 7 sul- Dyestuffs which dye cellulose material in similar shades phonic acid and 18 parts of sodium carbonate. The yelwith similar properties are obtained if the 5-nitro-3- low monoazo dyestufi so formed is isolated as described amino-2 hydroxybenzene-l-sulphonic acid is replaced by in Example 1 and coupled with the coupling product of 18.8 parts of 3-amino-4-hydroxybenzene-l-sulphonic acid the tetrazo compound from 24.4 parts of 4.4-diaminoamide or 22.3 parts of 5-chloro-4-hydroxy-3-aminoben- 3.3'-dimethoxy-dipheny1 and 31.9 parts of l-hydroxyzene-l-sulphonic acid and otherwise the same procedure naphthalene-3.8 disulphonic acid. The isolated trisazo is followed. dyestufi, when coppered in substance, dyes cotton and Example 4 l (JO-CH2 B018 03 01,110 ooH. I HO NH-GO- H'N=N --so.H H035 01H oi The diazo compound from 14.35 parts of 1-amino-2- staple fibre directly in strong blue-grey shades which have hydroXy-5-chlorobenzene is coupled in the presence of 18 good washing and water fastness properties and very good parts of sodium carbonate with 40.3 parts of l-acetofastness to light. The dyeings' are excellently stable to acetylamino-8-hydroxynaphthalene-3.6-disulphonic acid. anti-crease processing.

The yellow monazo dyestuif obtained in this matter is If in this example instead of 2-(3'-acetoacetylamino)- coupled as described in Example 1 with the coupling 0 henzoylamino 5 hydroxynaphthalene 7 sulphonic product of the tetrazo compound from 24.4 parts of 4.4'- acid, 44.2 parts of 2-(4'-acetoacetylamino)-benzoylaminodiamino3.3'-dimethoxydiphenyl and 31.9 parts of l-hy- 5-hydroxynaphthalene-7-sulphonic acid, 45.7 parts of 2- droxynaphthalene-3.S-disulphonic acid to form the trisazo (4 acetoacetylaminophenyl) carbamylamino 5 hydyestufi. The dyestufi, when treated in substance with droxynaphthalene-7-sulphonic acid or 45.7 parts of 2-(4- agents giving off copper, dyes cotton and regenerated acetoacetylaminophenyl) carbamylamino- 8 hydroxycellulose in reddish-grey shades. The dyeings have good naphthalene-S-sulphonic acid are used, then copper confastness to washing and light and are stable to anti-crease taining dyestuflfs which produce cellulose dyeings with processing. similar fastness properties are obtained.

' Example 6 OH O OCH OH on on =N N=N' NH-C O-\1JH-N=N ,QNH sofa Hots so,-cm

The diazo compound of 18.7 parts of 3-amino-4-hydroxybenzene-1-methy1 sulphone is coupled in an aqueous solution in the presence of 2;) parts of sodium carbonate with 32.3 parts of 2-acetoacetylamino-S-hydroxynaphtha- Hots on 01180 lene-6-sulphonic acid. The yellow monoazo dyestufi so formed is coupled under the same conditions as are given in Example 1 in the presence of sodium carbonate with the coupling product of the tetrazo compound of 24.4 parts of 4.4-diamino-3.3-dimethoxydiphenyl and 39.5 parts of 2-(3'-sulphophcnyl)-amino-5-hydroxynaphthalene-7-sulphonic acid to form the trisazo dyestutf. The copper complex compound obtained therefrom according to the method described in Example 1 dyes cotton and staple fibres directly in strong grey shades which have good wet fastness and good light fastness properties. The cellulose dyeings are distinguished by their very favorable behaviour to anti-crease processing.

I in this example the 2-(3-sulphophenyl)-amino-5- hydroxynaphthalene-7-sulphonic acid is replaced by 39.5 parts of 2-(3'-sulphophenyl)-amino-8-hydroxynaphthalene-6-sulphonic acid or 23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulphonic acid or 28.1 parts of 2-acetylamino-8-hydroxynapthalene-6-sulphonic acid or 28.1 parts of 2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid and otherwise the same procedure is followed, dye stuffs are obtained which dye cellulose material in blue to greenish-grey shades which have good fastness properties and also have excellent stability to anti-crease processing.

Example 7 H058 OH CHM) OCH: IOH

-N=N N=N HOsS- SOQH NH (LO OH CHs-C O(LH-N=N OzH The diazo compound from 18.9 parts of 3-amino-4- hydroxy-benzene-l-sulphonic acid is coupled in a soda alkaline medium with 24.3 parts of 1-acetoacety1amino-7- hydroxynaphthalene. The yellow monoazo dyestutf so obtained is converted in a soda alkaline solution into the trisazo dyestuff in the manner described in Example 1 with the coupling product of the tetrazo-compound from 244 parts of 4.4'-diamino-3.3'-dimethoxydiphenyl and 39.9 parts of l-hydroxynaphthalene3.6.8-trisulphonic acid. The trisazo dyestufi thus produced when coppered in substance dyes cotton and staple fibre directly'in bluegrey shades which have good washing and light fastness properties. The dyeings are very stable to anti-crease processing.

If the 39.9 parts of 1-hydroxynaphthalene-3.6.8-t1isula phonic acid are replaced by 31.9 parts of l-hydroxynaph- H038 OH Example 8 0 CH3 The yellow monoazo dyestulf formed from the diazo compound from 18.8 parts of 3-amino-4-hydroxybenzenel-sulphonic acid amide and a solution, containing sodium carbonate, of 32.3 parts of 2-acetoacetylamino-5-hydroxynaphthalene-7-sulphonic acid is isolated and converted at 90-95 in an aqueous solution into the corresponding copper complex compound with a mixture of 100 parts of a monomolar copper sulphate solution and 50 parts of a 20% ammonium hydroxide solution. This conversion takes 3 hours. The copper containing dyestuif in an aqueous solution is then coupled in the manner described in Example 1 with the coupling product of the tetrazo compound from 24.4 parts of 4.4'-diamino-3.3'-dimethoxydiphenyl and 31.9 parts of 1-hydroxynaphthalene-3.S-di sulphonic acid in a soda alkaline solution to form the trisazo dyestutf. The copper containing trisazo dyestutf so obtained dyes cotton in strong blue-grey shades which, on being after coppered, are fixed fast to Washing and water. The dyeings have very good light fastness. The coppered cellulose dyeings are very stable to anti-crease processing.

If instead of treating the yellow monoazo dyestuff described above with copper tetramine hydroxide in aqueous solution, it is converted into the corresponding cobalt complex compound at with 100 parts of a monomolar cobalt acetate solution and the cobalt complex compound is then coupled as described above to form the corresponding trisazo dyestutt and the cobalt containing dyestutt' is treated with agents giving olf copper, then a dyestutf containing cobalt and copper is obtained which also dyes cellulose fibres in strong blue-grey shades which have good fastness properties.

If in this example the 32.3 parts of 2-acetoacetylamino- 5-hydroxynaphthalene-7-sulphonic acid are replaced by 32.3 parts of 2-acetoacetylamino-6-hydr0xynaphthalene- 8-sulphonic acid, then with the same procedure the corresponding copper containing or cobalt and copper containing trisazo dyestulfs are obtained which dye cellulose material in neutral grey shades. The dyeings have good fastness to washing and light. These dyeings also are very stable to anti-crease processing.

Example 9 2 parts of the dyestufr obtained according to Example 1 are dissolved in a dyebath containing 3000 parts of Water and 2 parts of soda. 100 parts of cotton are entered at 40-50, the bath is heated within 30 minutes to -95", 30 parts of sodium sulphate are added and dyeing is performed for 45 minutes at this temperature. At the end of this time, the dyed goods are rinsed cold in the usual way and dried. The cotton is dyed in greenish-grey shades which have good wet fastness and very good light fastness properties.

What I claim is:

1. A trisazo dyestutf which corresponds to the formula ocm 0011,i

COCH: X

11 12 wherein --N=N-B--represents a member selected from Y represents a member selected from the group consistghe mu consisting of I v I ing of the direct linkage and the -NH--CO-Ph- 7 OH OH NH-CO--NH--Phand and ' radicals, wherein Ph represents a phenylene radlcal and HO Z represents a phenylamino radical, X represents a member selected from the group consisting of OH and COOH in o-position to the azo group, and D represents a radical 15 of the benzene series.

,3 2 A trisazo dyestufi which corresponds to the formula:

Hols OH amt OCH; 0H

N=N 2 (Jo-cm on a .7 s NH0o-0H-N=N- D lw H035 I V I BOzH wherein D represents a radical of the benzene series containing the hydroxyl group in ortho-position to the azo group. 30 3. A trisazo dyestuff having the formula:

H038 0H CHBO 00H; OH OH I (JO-CH:

N=N N=N NH-C OOHN=N SOzH Hogs I 4. A trisazo dyestufi having the formula:

Hols 011' Y 00133 OCH: OH OH I (JO-CH;

N =N N=N NH-C OCHN=N ogH Hols a is l a 0,011;

5. A trisazo dyestufi having the formula:

1103s OH OCH; ocrn' 0H OH -N=N N: -NH0 0-0 HN=N o1 sona I Hogs .6. A trisaz o dyestufihaving the formula:

Ems ocH, OCH:

7. A trisazo dyestufi having the formula: HOaIS OH OCH; (IJCH; 0H

SOaH

CO-GH:

NH-C 0--OHN=N 0211 References Cited in the file of this patent UNITED STATES PATENTS 521,095 Bernthsen et a1 June 5, 1894 561,694 Blank et a1 June 9, 1896 1,889,732 Stusser et a1 Nov. 29, 1932 

1. A TRISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 